Methods of recycling silicon swarf into electronic grade polysilicon or metallurgical-grade silicon

ABSTRACT

Methods of recycling silicon swarf into electronic grade polysilicon or metallurgical-grade silicon are described herein are described. In an example, a method includes cutting a silicon ingot and recovering silicon swarf having a first purity from the cutting process. The recovered silicon is purified in an upgraded metallurgical silicon process to produce electronic grade polysilicon particles having a second purity higher than the first purity. The upgraded metallurgical silicon process can include dissolving the recovered silicon particles in a molten aluminum metal smelt.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/500,350, filed Oct. 2, 2019, which is a 371 of International PatentApplication No. PCT/US2018/012831, filed Jan. 8, 2018, which claims thebenefit of U.S. Provisional Application No. 62/487,447, entitled “METHODOF RECYCLING SILICON SWARF INTO ELECTRONIC GRADE POLYSILICON,” filed onApr. 19, 2017, and U.S. Provisional Application No. 62/487,452, entitled“METHOD OF RECYCLING SILICON SWARF INTO METALLURGICAL GRADE SILICON,”filed on Apr. 19, 2017, the entire contents of which are herebyincorporated by reference herein.

TECHNICAL FIELD

Embodiments of the present invention are in the field of renewableenergy and, in particular, methods of recycling silicon byproducts.

BACKGROUND

The solar photovoltaic industry uses silicon wafers to buildphotovoltaic cells and modules. Photovoltaic cells, commonly known assolar cells, are well known devices for direct conversion of solarradiation into electrical energy. Generally, solar cells are fabricatedon a semiconductor wafer or substrate using semiconductor processingtechniques to form a p-n junction near a surface of the substrate. Solarradiation impinging on the surface of, and entering into, the substratecreates electron and hole pairs in the bulk of the substrate. Theelectron and hole pairs migrate to p-type and n-type doped regions inthe substrate, thereby generating a voltage differential between thedoped regions. The doped regions are connected to conductive regions onthe solar cell to direct an electrical current from the cell to anexternal circuit coupled thereto.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flowchart of a method of recycling silicon swarf to producehigh purity polysilicon, in accordance with an embodiment of the presentdisclosure.

FIG. 2 is a flowchart representing an ingot cutting process in a methodof recycling silicon swarf to produce high purity polysilicon, inaccordance with an embodiment of the present disclosure.

FIG. 3 is a flowchart representing an upgraded metallurgical siliconprocess in a method of recycling silicon swarf to produce high puritypolysilicon, in accordance with an embodiment of the present disclosure.

FIG. 4 is a flowchart of a method of recycling silicon swarf to producemetallurgical grade silicon particles, in accordance with an embodimentof the present disclosure.

FIG. 5 is a diagram of a centrifuge device for separating silicon swarf,in accordance with an embodiment of the present disclosure.

FIG. 6 is a chart illustrating purity levels of silicon particlesseparated from silicon swarf, in accordance with an embodiment of thepresent disclosure.

FIG. 7 is a pictorial view of a silicon aggregate in a centrifuge tube,in accordance with an embodiment of the present disclosure.

FIG. 8 is a pictorial view of metallurgical grade silicon particles, inaccordance with an embodiment of the present disclosure.

FIG. 9 illustrates graphs of particle size distributions in siliconswarf and metallurgical grade silicon particles, in accordance with anembodiment of the present disclosure.

FIG. 10 is a diagram of a silicon purification process usingmetallurgical grade silicon particles, in accordance with an embodimentof the present disclosure.

DETAILED DESCRIPTION

The following detailed description is merely illustrative in nature andis not intended to limit the embodiments of the subject matter or theapplication and uses of such embodiments. As used herein, the word“exemplary” means “serving as an example, instance, or illustration.”Any implementation described herein as exemplary is not necessarily tobe construed as preferred or advantageous over other implementations.Furthermore, there is no intention to be bound by any expressed orimplied theory presented in the preceding technical field, background,brief summary or the following detailed description.

This specification includes references to “one embodiment” or “anembodiment.” The appearances of the phrases “in one embodiment” or “inan embodiment” do not necessarily refer to the same embodiment.Particular features, structures, or characteristics may be combined inany suitable manner consistent with this disclosure.

Terminology. The following paragraphs provide definitions and/or contextfor terms found in this disclosure (including the appended claims):

“Comprising.” This term is open-ended. As used in the appended claims,this term does not foreclose additional structure or steps.

“Configured To.” Various units or components may be described or claimedas “configured to” perform a task or tasks. In such contexts,“configured to” is used to connote structure by indicating that theunits/components include structure that performs those task or tasksduring operation. As such, the unit/component can be said to beconfigured to perform the task even when the specified unit/component isnot currently operational (e.g., is not on/active). Reciting that aunit/circuit/component is “configured to” perform one or more tasks isexpressly intended not to invoke 35 U.S.C. § 112, sixth paragraph, forthat unit/component.

“First,” “Second,” etc. As used herein, these terms are used as labelsfor nouns that they precede, and do not imply any type of ordering(e.g., spatial, temporal, logical, etc.). For example, reference to a“first” solar cell does not necessarily imply that this solar cell isthe first solar cell in a sequence; instead the term “first” is used todifferentiate this solar cell from another solar cell (e.g., a “second”solar cell).

“Coupled”—The following description refers to elements or nodes orfeatures being “coupled” together. As used herein, unless expresslystated otherwise, “coupled” means that one element/node/feature isdirectly or indirectly joined to (or directly or indirectly communicateswith) another element/node/feature, and not necessarily mechanically.

In addition, certain terminology may also be used in the followingdescription for the purpose of reference only, and thus are not intendedto be limiting. For example, terms such as “upper”, “lower”, “above”,and “below” refer to directions in the drawings to which reference ismade. Terms such as “front”, “back”, “rear”, “side”, “outboard”, and“inboard” describe the orientation and/or location of portions of thecomponent within a consistent but arbitrary frame of reference which ismade clear by reference to the text and the associated drawingsdescribing the component under discussion. Such terminology may includethe words specifically mentioned above, derivatives thereof, and wordsof similar import.

“Inhibit”—As used herein, inhibit is used to describe a reducing orminimizing effect. When a component or feature is described asinhibiting an action, motion, or condition it may completely prevent theresult or outcome or future state completely. Additionally, “inhibit”can also refer to a reduction or lessening of the outcome, performance,and/or effect which might otherwise occur. Accordingly, when acomponent, element, or feature is referred to as inhibiting a result orstate, it need not completely prevent or eliminate the result or state.

Efficiency is an important characteristic of a solar cell as it isdirectly related to the capability of the solar cell to generate power.Likewise, efficiency in producing solar cells is directly related to thecost effectiveness of such solar cells. Accordingly, techniques forincreasing the efficiency of solar cells, or techniques for increasingthe efficiency in the manufacture of solar cells, are generallydesirable. Some embodiments of the present disclosure allow forincreased solar cell manufacture efficiency by providing novel processesfor fabricating solar cell structures. Some embodiments of the presentdisclosure allow for increased solar cell efficiency by providing novelsolar cell structures.

Methods of recycling silicon swarf into electronic grade polysilicon ormetallurgical-grade silicon are described herein. In the followingdescription, numerous specific details are set forth in order to providea thorough understanding of embodiments of the present disclosure. Itwill be apparent to one skilled in the art that embodiments of thepresent disclosure can be practiced without these specific details. Inother instances, well-known fabrication techniques, such as approachesto forming solar cells from individual wafers cut from ingots, are notdescribed in detail in order to not unnecessarily obscure embodiments ofthe present disclosure. Furthermore, it is to be understood that thevarious embodiments shown in the figures are illustrativerepresentations and are not necessarily drawn to scale.

Disclosed herein are methods of recycling silicon byproducts. In oneembodiment, a method includes cutting a silicon ingot and recoveringsilicon swarf having a first purity from the cutting process. Therecovered silicon is purified in an upgraded metallurgical siliconprocess to produce electronic grade polysilicon particles having asecond purity higher than the first purity. The upgraded metallurgicalsilicon process can include dissolving the recovered silicon particlesin a molten aluminum metal smelt.

In another embodiment, a method includes cutting a silicon ingot andrecovering silicon swarf from the cutting process. The recovered siliconswarf can be compacted into a silicon aggregate, and the siliconaggregate can be dehydrated to form metallurgical grade siliconparticles. The metallurgical grade silicon particles can have apredetermined particle size that is suitable for handling. Themetallurgical grade silicon particles can be introduced into apurification process to produce electronic grade polysilicon particles.

Silicon wafers can be cut from silicon ingots. Slicing ingots intowafers typically involves sawing a silicon ingot, e.g., using adiamond-wire sawing process.

In a first aspect, the sawing process can produce byproducts, such assilicon particles, also known as silicon swarf. The silicon swarfrepresents a value loss unless the byproduct can be recaptured forfuture use. Attempts at harvesting and recycling silicon swarf for usein photovoltaic (PV) cells and modules include reintroducing siliconswarf into a conventional Siemens or Fluidized Bed Reactor (FBR)process. Those processes are energy intensive, however, and have notbeen shown to reliably produce recycled ingots having a level of purityrequired for high-efficiency solar cell applications. More particularly,the economic viability of using conventional recycling processes toproduce electronic grade silicon from silicon swarf is unproven.

In accordance with an embodiment of the present disclosure, a method ofrecycling silicon swarf to produce high purity electronic gradepolysilicon particles is provided. Silicon swarf produced by an ingotcutting process can be refined by an upgraded metallurgical siliconprocess to remove contaminants and increase a purity of the siliconswarf. The upgraded metallurgical silicon process can include dissolvingrecovered silicon particles in a molten aluminum metal smelt. Theprocess can be less energy intensive, and more particularly, can reducethe need for fossil fuel-based energy inputs, as compared toconventional Siemens or FBR processes. Accordingly, silicon swarfrecycled by the processes described below can bring silicon byproductsback into the PV value stream in a cost-effective and environmentallysustainable manner.

Referring to FIG. 1 , a flowchart 100 of a method of recycling siliconswarf to produce high purity polysilicon is shown, in accordance with anembodiment of the present disclosure. Single crystal ingots (typicallyreferred to as boules) of materials are grown (e.g., by crystal growth)using methods such as the Czochralski process or Bridgeman technique.The boules can be used to produce silicon wafers for use in, e.g., solaror other industries such as the electronic industry. Multicrystallinesilicon ingots can also be used to form wafers for various applications.Ingots are typically manufactured by the freezing of a molten liquid(often referred to as the melt) in a mold. The manufacture of ingots ina mold is designed to completely solidify and form an appropriate grainstructure required for later processing, since the structure formed bythe freezing melt controls the physical properties of the material.Furthermore, the shape and size of the mold is designed to allow forease of ingot handling and downstream processing. Typically, the mold isdesigned to minimize melt wastage and aid ejection of the ingot, aslosing either melt or ingot increases manufacturing costs of finishedproducts. The physical structure of a crystalline material is largelydetermined by the method of cooling and precipitation of the moltenmetal.

A crystalline silicon ingot can have predetermined doping andresistivity characteristics. For example, a silicon ingot can have abulk silicon resistivity in a range of 1-10 Ω-cm. The resistivity cancorrespond to a dopant incorporated into the silicon ingot. For example,the silicon ingot can include a p-type dopant, such as boron, indium,aluminum, or gallium. Alternatively, the silicon ingot can include ann-type dopant, such as phosphorus, arsenic, or tin. A purity of thesilicon ingot, excluding the dopant materials, can be higher than 10 N,e.g., 11 N. The purity can be achieved through an Upgraded MetallurgicalGrade silicon (UMG-Si) process or another silicon purification and/oringot formation process.

At operation 102, the silicon ingot is cut to divide the ingot into awafer portion, and uncut portion, and a silicon swarf. Differentapproaches have been used to slice ingots into wafers, e.g., into singlecrystalline silicon wafers. A common approach involves beam handling ofthe ingot. Beamless ingot slicing approaches are also used. An exampleof an ingot cutting process is described below, by way of example, andnot a limitation.

Referring to FIG. 2 , a flowchart 200 representing an ingot cuttingprocess in a method of recycling silicon swarf to produce high puritypolysilicon is shown, in accordance with an embodiment of the presentdisclosure. At operation 202, a portion of the ingot is held. Forexample, the ingot can be held to a resin beam material using a glue.Alternatively, the ingot may be gripped by a gripper. At operation 204,the ingot is partially cut to form several wafer portions projectingfrom an uncut portion of the ingot. For example, diamond embeddednickel-plated wires from a wire saw are used to cut wafer shapes intothe ingot. In an embodiment, the extent of cutting is suitable toultimately provide symmetrical wafers cut from the ingot. At operation206, the ingot also includes further cutting the ingot in a directionorthogonal to the direction of cutting of operation 204. For example,the cutting of operation 204 can be transverse to a longitudinal axis ofthe ingot, and the cutting of operation 206 can be parallel to thelongitudinal axis. Such cutting in the orthogonal direction is used toseparate the wafer portions from the uncut portion, providing aplurality several discrete wafers.

In an embodiment, both partially cutting (operation 204) and furthercutting (operation 206) the ingot includes using a same wire cuttingtechnique such as, but not limited to, diamond-wire (DW) cutting andslurry-based wire slicing processes. A DW cutting process is a processof using wire of various diameters and lengths, impregnated with finediamond particles of various pre-selected sizes and shapes to cutthrough materials. Slurry-based wire saws for slurry slicing typicallyuse bare wire and include the cutting material (e.g., silicon carbide,SiC) in the cutting fluid (e.g., polyethylene glycol, PEG). By contrast,DW cutting typically does not use loose abrasives but rather onlycoolant fluid (either water-based or glycol-based) to lubricate, coolthe cut, and remove debris.

A wire saw can refer to a machine using a metal wire or cable forcutting. There are typically two types of wire saw movements, namelycontinuous (or endless or loop) and oscillating (or reciprocating). Thewire can have one strand or many strands braided together. The wire sawuses abrasives to cut. Depending on the application, diamond materialmay or may not be used as an abrasive, as described above. Asingle-strand saw can be roughened to be abrasive, abrasive compoundscan be bonded to the cable, or diamond-impregnated beads (and spacers)can be threaded on the cable.

Thus, in an exemplary embodiment, in the case of a mono-crystallinesilicon ingot, an initially round ingot undergoes a cutting process todivide the silicon ingot into one or more wafer portions. As a byproductof the sawing technique, e.g., a DW cutting process, fine particles ofsilicon can be ejected from the cutting path by the saw wire or blade.These particles are analogous to sawdust. The silicon material may mixwith one or more additional byproducts from the cutting process in amixture referred to as silicon swarf. For example, silicon swarf caninclude silicon particles and one or more contaminants, such as metaldebris or coolant additives. The contaminants can mix with the siliconparticles during the cutting process. For example, the coolant additivescan come from a cutting fluid used during the sawing process. It is tobe appreciated that the cooling additives and/or cooling fluid may berecovered for reuse or recycling.

Referring again to FIG. 1 , at operation 104, the silicon swarf isfiltered to recover silicon particles from the silicon-contaminantmixture. In an embodiment, the silicon swarf is filtered to separate theone or more contaminants from the silicon particles that, afterfiltering, can be referred to as recovered silicon particles. Thecontaminants can be effectively removed using a low-cost filtrationprocess. For example, the silicon swarf can be filtered by a porouscloth or membrane to pass one of the silicon particles or thecontaminants, and retain the other of the silicon particles or thecontaminants. The recovered silicon particles can have a first purity.For example, after filtering, the recovered silicon particles can have apurity less than 4 N, e.g., 1-3 N. More particularly, the first puritycan be in a range of 98-99.9% Si. It will be recognized that the firstpurity of the recovered silicon particles can be lower than a purity ofthe silicon ingot. Accordingly, the recovered silicon particles canrequire additional refinement prior to being used in an ingot formationprocess.

At operation 106, the recovered silicon particles are purified toproduce electronic grade polysilicon particles. The recovered siliconparticles can be introduced as metallurgical grade silicon feedstockmaterial for an upgraded metallurgical grade silicon process. An exampleof the upgraded metallurgical silicon process is described below.

Referring to FIG. 3 , a flowchart 300 representing an upgradedmetallurgical silicon process in a method of recycling silicon swarf toproduce high purity polysilicon is shown, in accordance with anembodiment of the present disclosure. The recovered silicon particlesprovide a starting material having a known electrical resistivity forthe upgraded metallurgical silicon process. For example, the resistivityof the recovered silicon starting material can be the same as theresistivity of the silicon ingot. Similarly, the recovered siliconstarting material may have a same doping, e.g., p-type or n-typedopants, and thus, may be considered to be pre-doped. At operation 302,the recovered silicon particles are dissolved in a molten aluminum metalsmelt. The recovered silicon particles can be dissolved at temperaturesbelow 1,000° C. Accordingly, a molten solution of the recovered siliconparticles and an aluminum material can be formed.

At operation 304, the molten aluminum metal smelt can be solidified toseparate the solution into a master alloy (an aluminum-silicon alloy)and solar silicon flakes. The solar silicon flakes can have an outersurface, and aluminum material can be present on the outer surface. Thesilicon material forming the solar silicon flakes, however, can have apurity higher than the first purity of the recovered silicon particles.For example, the purity of the solar silicon flakes, excluding dopantsand aluminum coating materials, can be higher than 3 N.

At operation 306, the solar silicon flakes are washed with an acid. Forexample, hydrochloric acid can be applied to the solar silicon flakes toremove the aluminum material on the outer surface of the flakes. Afterwashing the solar silicon flakes, the flakes can be referred to aselectronic grade polysilicon particles. More particularly, theelectronic grade polysilicon particles can have a second purity,excluding any dopant materials, higher than the first purity of therecovered silicon particles. The second purity can be higher than 10 N,e.g., 11 N. More particularly, the silicon purity of the electronicgrade polysilicon particles can be 99.99999999% Si. A purity of theelectronic grade polysilicon particles, including any dopant materials,can be less than 10 N, e.g., 7N.

The electronic grade polysilicon particles can have a same resistivityas the silicon ingot. For example, the electronic grade polysiliconparticles can have a resistivity in a range of 1-10 Ω-cm. Similarly, theelectronic grade polysilicon particles can be pre-doped with the samedopant incorporated into the silicon ingot. By way of example, theelectronic grade polysilicon particles can include a p-type dopant, suchas boron, indium, aluminum, or gallium. Alternatively, the electronicgrade polysilicon particles can include an n-type dopant, such asphosphorus, arsenic, or tin.

At operation 308, the electronic grade polysilicon particles can betransformed into a recovered silicon ingot. For example, the electronicgrade polysilicon particles can be melted and cast in a mold to form therecovered silicon ingot having a size, shape, and material identical tothe silicon ingot used to produce the silicon swarf. Accordingly, therecovered silicon ingot can be further processed, e.g., by DW cutting,to produce more wafer portions.

It will be recognized that the recovered silicon particles or theelectronic grade polysilicon particles described above can be introducedinto a solar cell production line at various stages. For example,depending on the material characteristics, e.g., the material type,purity, etc., the particles can be used as feedstock material at a slagtreatment stage, a leaching stage, or a solidification stage of a solarsilicon production line. Accordingly, the above description is to beviewed in an illustrative sense and not a restrictive sense.

In an embodiment, a solar cell is fabricated from one of the waferportions formed from the recovered silicon ingot. For example, a PV cellcan be formed using a mono-crystalline silicon wafer fabricated by abeamless slicing methodology applied to the recovered silicon ingot. PVcells, commonly known as solar cells, are well known devices for directconversion of solar radiation into electrical energy. Generally, solarcells are fabricated on a semiconductor wafer or substrate usingsemiconductor processing techniques to form a p-n junction near asurface of the substrate. Solar radiation impinging on the surface of,and entering into, the substrate creates electron and hole pairs in thebulk of the substrate. The electron and hole pairs migrate to p-dopedand n-doped regions in the substrate, thereby generating a voltagedifferential between the doped regions. The doped regions are connectedto conductive regions on the solar cell to direct an electrical currentfrom the cell to an external circuit coupled thereto. It is to beunderstood, however, that the above silicon recycling process is notlimited to generating wafers for solar cell fabrication.

In another aspect, the sawing process can produce byproducts, such as aslurry of silicon particles and contaminants, also known as siliconswarf. Attempts at harvesting and recycling silicon swarf for use inphotovoltaic (PV) cells and modules include reintroducing silicon swarfinto a polysilicon manufacturing process, e.g., a conventional Siemensprocess. Prior attempts at recovering silicon particles from the siliconswarf, however, have only been successful in recovering fine siliconpowder having an average particle size of less than 1 micron. Finesilicon powder is difficult to handle and is not readily useful as afeedstock material for polysilicon manufacturing processes. Moreparticularly, the fine silicon powder is suboptimal for the purposes oftransportation and as direct feedstock as metallurgical-grade silicon(MG-Si) for Siemens-based polysilicon manufacturing.

It will be appreciated that, although the description relates primarilyto recycling silicon swarf for use in PV cells and modules, therecycling of silicon swarf has much broader application. For example,recycled silicon swarf and/or byproducts of recycling silicon swarf canbe used in silicone and aluminum alloy applications. The industries thatcan benefit from the methods described below, and more particularly,from the product of silicon swarf recycling, include the automotive,aerospace, and building materials sectors.

In accordance with an embodiment of the present disclosure, a method ofrecycling silicon swarf to produce MG-Si particles is provided. Siliconswarf produced by an ingot cutting process can be compacted into asilicon aggregate, and the silicon aggregate can be dehydrated to formMG-Si particles. The MG-Si particles can have a particle size at leastan order of magnitude larger than a particle size of silicon particlesin the silicon swarf. For example, a majority of the MG-Si particlesresulting from the recycling process can have a particle size greaterthan 50 microns, e.g., in a range of 50 microns to 10 mm. The MG-Siparticles can be further processed, e.g., ground, and selected based onsize. The selected MG-Si particles can be introduced into a polysiliconmanufacturing process to produce a recycled silicon ingot for furthersilicon wafer production. Unselected MG-Si particles can be reintroducedinto the recycling process and recovered.

Referring to FIG. 4 , a flowchart 400 of a method of recycling siliconswarf to produce metallurgical grade silicon particles is shown, inaccordance with an embodiment of the present disclosure. Single crystalingots (typically referred to as boules) of materials are grown (e.g.,by crystal growth) using methods such as the Czochralski process orBridgeman technique. The boules can be used to produce silicon wafersfor use in, e.g., solar or other industries such as the electronicindustry. Multicrystalline silicon ingots can also be used to formwafers for various applications. Ingots are typically manufactured bythe freezing of a molten liquid (often referred to as the melt) in amold. The manufacture of ingots in a mold is designed to completelysolidify and form an appropriate grain structure required for laterprocessing, since the structure formed by the freezing melt controls thephysical properties of the material. Furthermore, the shape and size ofthe mold is designed to allow for ease of ingot handling and downstreamprocessing. Typically, the mold is designed to minimize melt wastage andaid ejection of the ingot, as losing either melt or ingot increasesmanufacturing costs of finished products. The physical structure of acrystalline material is largely determined by the method of cooling andprecipitation of the molten metal.

A crystalline silicon ingot can have predetermined doping andresistivity characteristics. For example, a silicon ingot can have abulk silicon resistivity in a range of 1-10 Ω-cm. The resistivity cancorrespond to a dopant incorporated into the silicon ingot. For example,the silicon ingot can include a p-type dopant, such as boron, indium,aluminum, or gallium. Alternatively, the silicon ingot can include ann-type dopant, such as phosphorus, arsenic, or tin. A purity of thesilicon ingot, excluding dopant materials, can be higher than 10 N,e.g., 11 N. The purity can be achieved through an Upgraded MetallurgicalGrade silicon (UMG-Si) process or another silicon purification and/oringot formation process.

At operation 402, the silicon ingot is cut to divide the ingot into awafer portion and a silicon swarf. Different approaches have been usedto slice ingots into wafers, e.g., into single crystalline siliconwafers. A common approach involves beam handling of the ingot. Beamlessingot slicing approaches are also used. In an embodiment, an example ofan ingot cutting process is in a in a method of recycling silicon swarfto produce metallurgical grade silicon particles is the same as orsimilar to the process described above in association with flowchart 200of FIG. 2 .

In an example, the resulting silicon swarf can include a mixture ofsilicon particles and one or more contaminants. The contaminants can bemetal debris or liquid waste, by way of example. More particularly, theliquid waste may include coolant additives from a cutting fluid that mixwith the silicon particles during the cutting process. The cutting fluidcan be a diluted water-based coolant, and can account for 0.5-4% volumeof the silicon swarf. It is to be appreciated that cooling additivesand/or cooling fluid may be recovered for reuse or recycling.

To recover the silicon particles from the silicon swarf for use in apolysilicon manufacturing process, the liquid waste can be separatedfrom the silicon particles. Referring again to FIG. 4 , at operation404, the silicon swarf is compacted into a silicon aggregate. Compactionof the silicon swarf can separate the liquid waste from the siliconparticles as described below. For example, compacting silicon swarf caninclude centrifuging the silicon swarf such that the silicon particlesspin to an outer region of a centrifuge tube and separate from theliquid waste.

Referring to FIG. 5 , a diagram of a centrifuge device 500 forseparating silicon swarf is shown, in accordance with an embodiment ofthe present disclosure. Silicon swarf 502 is introduced as a feedsuspension into a centrifuge tube 504 of centrifuge device 500.Centrifuge device 500 may be a device for performing decantercentrifugation, for example, which includes centrifuge tube 504.Centrifuge tube 504 may be surrounded by an imperforate bowl 506 whichis formed by an outer coating 508. Centrifuge tube 504 can be spun by amotor 510, causing heavier silicon particles to spin outward againstcentrifuge tube 504 and form a cake 512 on a wall of centrifuge tube504. Cake 512 may be referred to as a silicon aggregate. The siliconaggregate can have microscopic level compaction. However, particleswithin the aggregate may still be in a powder form. Liquid(s) 514 may beremoved according to the flow of the arrows of FIG. 5 and ultimatelyaccumulated as a centrate 516.

Referring to FIG. 6 , a chart 600 illustrates purity levels of siliconparticles separated from silicon swarf is shown, in accordance with anembodiment of the present disclosure. In an embodiment, the siliconparticles of silicon swarf are separated from the liquid waste usingnon-centrifuge techniques. For example, the silicon swarf can befiltered by a porous cloth or a membrane to remove the liquid waste andobtain the silicon aggregate. The data of FIG. 6 indicates that there isno significant difference between different separation methods in termsof a purity of the separated silicon particles. Specifically, thesilicon aggregate, as achieved by any of the separation methods ofstandard centrifugation, ultra-centrifugation, cloth filtration, ormembrane filtration, have silicon purity (excluding carbon and oxygen)of 3N. More particularly, the silicon particles extracted from thesilicon swarf can have a purity of 99.9% Si. Typical metallurgic grademetal levels are shown in region 602 of chart 600.

Referring to FIG. 7 , a pictorial view of a silicon aggregate in acentrifuge tube 702 is shown, in accordance with an embodiment of thepresent disclosure. Centrifuging a silicon swarf can deposit the siliconparticles in the silicon swarf onto an inner channel 704 of a tube wall706 of centrifuge tube 702. The deposited silicon aggregate 708 may havea moisture content less than a moisture content of the silicon swarf.For example, silicon aggregate 708 can have a moisture content of40-50%, e.g., 45%. The compacted silicon aggregate 708 can have asilicon volume density in a range of 50-60%, e.g., 55%. Depending on thecentrifugation force during such process, the compaction of siliconswarf can simultaneously form larger silicon particles. For example, thecompacted silicon particles may be discrete particles having sizes ofgreater than 100 μm in diameter.

Referring again to FIG. 4 , at operation 406, a silicon aggregate isdehydrated to form MG-Si particles. Dehydration of the silicon aggregatecan be performed by a furnace. For example, the centrifuge tubecontaining the silicon aggregate may be placed in a furnace having anelevated temperature, e.g., 250° C., for a predetermined period of time.Heating of the silicon aggregate can cause moisture in the siliconaggregate, e.g., organic residues left over from the cutting fluid, toevaporate.

Referring to FIG. 8 , a pictorial view of metallurgical grade siliconparticles 800 is shown, in accordance with an embodiment of the presentdisclosure. The heating process at operation 406 can also cause thesilicon aggregate to agglomerate into metallurgical-grade silicon(MG-Si) particles 800. In an embodiment, MG-Si particles 800 resultingfrom the dehydration process have substantially different bulkproperties than the silicon aggregate 708 of FIG. 7 . For example, themoisture content of silicon aggregate 708 can be at least twice amoisture content of MG-Si particles 800. By way of example, the moisturecontent of MG-Si particles 800 can be less than 2%, e.g., 0.11%.Accordingly, the moisture content of MG-Si particles 800 can be at leastan order of magnitude less than silicon aggregate 708 of FIG. 7 .

Referring to FIG. 9 , graphs 900 and 902 of particle size distributionsin silicon swarf and metallurgical grade silicon particles,respectively, is shown, in accordance with an embodiment of the presentdisclosure. It is to be appreciated that particle size as usedthroughout the description can refer to an average maximum dimension ofa particle as determined by known sizing techniques. Particles may notbe perfectly spherical, and thus, may not have diameters in a technicalsense, however, a particle size may be expressed as a diameter oranother dimensional standard known in the art.

A particle size of MG-Si particles 800 may also differ substantiallyfrom the particle size of silicon aggregate 708. In an embodiment, arange of particle sizes of the silicon particles in as-sawn siliconswarf is less than 1 micron. As described above, silicon particles insilicon aggregate 708 can have substantially a same size as the as-sawnsilicon swarf. By contrast, a majority of MG-Si particles 800 resultingfrom a centrifugation compacting 904 and a dehydration process 906 havea particle size at least an order of magnitude greater than the particlesize of the as-sawn silicon particles. For example, in an embodiment,MG-Si particles 800 have a particle size greater than 40 microns, and amajority of the MG-Si particles have a particle size greater than 50microns. Most of MG-Si particles 800 may have sizes in a range of 70-100microns or even larger. Accordingly, MG-Si particles 800 produced by thecentrifugation and dehydration processes can be well-suited to handlingas compared to silicon powder generated by a diamond wire (DW) cuttingprocess.

In an embodiment, a method of recycling silicon swarf can optionallyinclude operations to make the size of MG-Si particles introduced into apolysilicon manufacturing process more uniform. Referring again to FIG.4 , at operation 408, MG-Si particles 800 can be ground to reduce amaximum size of the MG-Si particle distribution below a predeterminedthreshold. For example, MG-Si particles 800 can be passed through aball-milling process, or another grinding process, to reduce theparticle size of MG-Si particles 800 to less than 1000 micron, e.g., ina range of 100-1000 micron. In an embodiment, the maximum particles sizeis reduced to less than 1 micron.

Referring again to FIG. 4 , in addition to altering a size of the MG-Siparticles resulting from the dehydration process, MG-Si particles of apredetermined size range may be selected for introduction into thepolysilicon manufacturing process. For example, at operation 410, afirst subset of the MG-Si particles can be separated from a secondsubset of the MG-Si particles. In an embodiment, the first subsetincludes MG-Si particles having a predetermined minimum size. Forexample, the first subset may include MG-Si particles having a particlesize of at least 1 micron. The second subset of MG-Si particles, whichdoes not meet the minimum size threshold, may be reintroduced into therecycling method at operation 404. That is, the second subset of MG-Siparticles may be mixed with the silicon swarf and reintroduced into thecentrifugation process. Accordingly, compaction and dehydration ofsilicon particles from the silicon swarf can be processed in a loopuntil they are agglomerated into an MG-Si particle meeting the minimumsize threshold for further processing in the polysilicon manufacturingprocess.

Referring again to FIG. 4 , at operation 412, the MG-Si particles can bepurified into electronic grade polysilicon particles. The MG-Siparticles can be optimally sized for transportation and for use asdirect feedstock to manufacture polysilicon in a silicon purificationprocess.

Referring to FIG. 10 , a diagram of a silicon purification process 1000using metallurgical grade silicon (MG-Si) particles 1002 is shown, inaccordance with an embodiment of the present disclosure. Themetallurgical grade silicon particles 1002, e.g., as produced byoperations 402-410 of the flowchart 400 of FIG. 4 can be introducedinto, for example, a Siemens-based polysilicon manufacturing process ata stage that normally uses metallurgical grade silicon particles 1002produced by a silicon dioxide reduction process. In an embodiment,metallurgical grade silicon particles 1002 have a first purity, e.g., ina range of 2-4 N, such as 3 N. More particularly, in one embodiment,metallurgical grade silicon particles 1002 introduced into the siliconpurification process can have a first purity of 99-99.9% Si. Themetallurgical grade silicon particles 1002 can be purified through aseries of processes, e.g., trichlorosilane processes etc. as describedin greater detail below, to further refine and remove impurities in themetallurgical grade silicon particles 1002. In an embodiment, afterapplying silicon purification processes to the metallurgical gradesilicon particles 1002, the metallurgical grade silicon particles 1002may be transformed into electronic grade polysilicon particles 1004having a second purity higher than the first purity.

In an embodiment, the second purity of the electronic grade polysiliconparticles 1004 is suitable for ingot growing 1006 and/or block casting1008 and/or cylinder growing 1010. For example, the second purity may behigher than 10 N, e.g., 99.99999999% Si. Accordingly, the electronicgrade polysilicon particles 1004 may be further processed to form arecycled silicon ingot having the same or essentially the same materialproperties as the silicon ingot used to form silicon swarf at operation402 of flowchart 400 of FIG. 4 . The recycled silicon ingot may besubjected to wafer cutting 1012 in an overall silicon wafer fabricationprocess 1014. That is, the recycled silicon swarf may be effectivelyreintroduced into a photovoltaic (PV) silicon value chain asmetallurgical grade silicon particles 1002 that are precursor materialto recycled silicon ingots. It is to be appreciated that metallurgicalgrade silicon can be expensive, and thus, the recapture of siliconparticles that would otherwise be lost as silicon swarf reduces anoverall all-in silicon cost and realizes an economic benefit.

Referring again to FIG. 10 , in an embodiment, a purification processmay include a silicon dioxide reduction operation 1016. An SiO₂ source1018 and a carbon source 1020 are subjected to an electronic arc furnace1022 at a temperature in the range of 1900-2000 degrees Celsius.

Referring again to FIG. 10 , in an embodiment, a purification processmay include a chemical Si purification operation 1024. A hydrochloricacid source 1026 is combined with product 1028 from the silicon dioxidereduction operation 1016 in a fluid bed reactor (FBR) 1030. At fluid bedreactor (FBR) 1030, hydrogen gas (H2) 1032 may be expelled.Trichlorosilane (SiHCl3) 1034 is produced, and is subjected to dustfiltration 1036, and a trichlorosilane condensation operation 1038. Theresulting product is then held in a trichlorosilane storage tank 1040,and ultimately distilled at distillation stages 1042. The resultingpurified trichlorosilane product 1044 is processed through an Sievaporator 1046 where hydrogen (H2) 1048 is introduced. The resultingproduct is then processed through a chemical vapor deposition (CVD)reactor 1050 to product electronic grade polysilicon particles 1004 anda vent gas 1052.

In an embodiment, a solar cell is fabricated from one of the waferportions formed from the recycled silicon ingot. For example, a PV cellcan be formed using a mono-crystalline silicon wafer fabricated by abeamless slicing methodology applied to the recycled silicon ingot. PVcells, commonly known as solar cells, are well known devices for directconversion of solar radiation into electrical energy. Generally, solarcells are fabricated on a semiconductor wafer or substrate usingsemiconductor processing techniques to form a p-n junction near asurface of the substrate. Solar radiation impinging on the surface of,and entering into, the substrate creates electron and hole pairs in thebulk of the substrate. The electron and hole pairs migrate to p-dopedand n-doped regions in the substrate, thereby generating a voltagedifferential between the doped regions. The doped regions are connectedto conductive regions on the solar cell to direct an electrical currentfrom the cell to an external circuit coupled thereto. It is to beunderstood, however, that the above silicon recycling process is notlimited to generating wafers for solar cell fabrication.

Thus, methods of recycling silicon byproducts have been disclosed.

Although specific embodiments have been described above, theseembodiments are not intended to limit the scope of the presentdisclosure, even where only a single embodiment is described withrespect to a particular feature. Examples of features provided in thedisclosure are intended to be illustrative rather than restrictiveunless stated otherwise. The above description is intended to cover suchalternatives, modifications, and equivalents as would be apparent to aperson skilled in the art having the benefit of the present disclosure.

The scope of the present disclosure includes any feature or combinationof features disclosed herein (either explicitly or implicitly), or anygeneralization thereof, whether or not it mitigates any or all of theproblems addressed herein. Accordingly, new claims may be formulatedduring prosecution of the present application (or an applicationclaiming priority thereto) to any such combination of features. Inparticular, with reference to the appended claims, features fromdependent claims may be combined with those of the independent claimsand features from respective independent claims may be combined in anyappropriate manner and not merely in the specific combinationsenumerated in the appended claims.

What is claimed is:
 1. A method of purifying silicon, the methodcomprising: subjecting silicon particles having a first purity to asilicon dioxide reduction operation to form a first product; combiningthe first product with a hydrochloric acid source in a fluid bed reactorand expelling hydrogen gas at the fluid bed reactor to formtrichorosilane; subjecting the trichlorosilane to a dust filtrationprocess; subsequent to subjecting the trichlorosilane to the dustfiltration process, subjecting the trichlorosilane to a trichlorosilanecondensation process to form a second product; distilling the secondproduct to form purified trichlorosilane; processing the purifiedtrichlorosilane through a silicon evaporator and introducing hydrogen toform a third product; and processing the third product through achemical vapor deposition reactor to form silicon particles having asecond purity greater than the first purity.
 2. The method of claim 1,wherein the first purity is metallurgical grade.
 3. The method of claim2, wherein the second purity is electronic grade.
 4. The method of claim1, wherein the second purity is electronic grade.
 5. The method of claim1, wherein the second purity is greater than 10N.
 6. The method of claim1, further comprising: forming an ingot from the silicon particleshaving the second purity.
 7. The method of claim 1, wherein the siliconparticles having the first purity include a p-type dopant.
 8. The methodof claim 1, wherein the silicon particles having the first purityinclude an n-type dopant.
 9. The method of claim 2, wherein the firstpurity is less than 4N.